Coated granular fertilizers, methods of manufacture thereof, and uses

ABSTRACT

A coated fertilizer comprises a fertilizer granule; and a coating disposed on a surface of the fertilizer granule, wherein the coating comprises a poly(lactic acid); a second polymer comprising a poly(butylene succinate), a cellulose triacetate, or a combination comprising at least one of the foregoing; and a sealant. Methods of making the coated fertilizer are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This Application claims the benefit of U.S. Provisional Application No.61/988,459, filed on May 5, 2014, which is incorporated herein byreference in its entirety.

BACKGROUND

This disclosure is directed to coated granular fertilizers, theirmethods of manufacture, and methods of use.

Granular fertilizers can be coated to reduce dust production and to slowthe release of nutrients into the soil. However, commercial productssuch as sulfur-coated urea, polyurethane-coated urea, and polyethylenecoated-urea have certain drawbacks. For example, sulfur coatings canincrease the acidity of soil by forming sulfuric acid upon degradationof the coating. Because the sulfur coatings and the polyethylenecoatings generally do not contain nitrogen, the overall nitrogen contentof the fertilizer on a weight basis is decreased. The polyurethane andthe polyethylene coatings are not readily biodegradable, and thus onlypartially decompose or do not decompose at all. These coating materialsor the residues thereof can therefore accumulate in soil over time, withpotentially adverse results. Accordingly, improved fertilizer coatingsare continuously sought, in particular fertilizer coatings that arebiodegradable. It would be a further advantage if the fertilizercoatings did not adversely affect soil conditions over time, and itwould be an even further advantage if a high weight basis of nitrogenwas maintained.

SUMMARY

In a first embodiment, a coated fertilizer comprises a fertilizergranule; and a coating disposed on a surface of the fertilizer granule,wherein the coating comprises a poly(lactic acid); a second polymercomprising a poly(butylene succinate), a cellulose triacetate, or acombination comprising at least one of the foregoing; and a sealant.

A method of manufacture of the coated fertilizer of the first embodimentcomprises combining the poly(lactic acid), the second polymer, and thesealant to provide a coating composition; and depositing the coatingcomposition as a layer on a plurality of fertilizer granules to providethe coated fertilizer.

Alternatively, a method of manufacture of the coated fertilizer of thefirst embodiment comprises dissolving the poly(lactic acid) and thesecond polymer in a solvent to provide a solution; depositing thesolution on a fertilizer granule to form a first layer; and depositing asealant on the first layer to form a second layer.

In a second embodiment, a coated fertilizer comprises: a fertilizergranule; and a coating disposed on the fertilizer granule, wherein thecoating comprises lignin, starch acetate, or a combination thereof; anda second polymer comprising a poly(lactic acid), a poly(butylenesuccinate), a cellulose triacetate, a poly(caprolactone), apoly(butylene terephthalate adipate), a cellulose acetate, or acombination comprising at least one of the foregoing. For example, thecoating comprises: a first layer disposed on the fertilizer granule,wherein the first layer comprises the lignin, starch acetate, orcombination thereof; a second layer disposed on the first layer, whereinthe second layer comprises one or more second polymers; and optionally,a third layer, wherein the third layer comprises an additional secondpolymer. Optionally the coating further comprises a sealant.

A method of making the coated fertilizer of the second embodimentcomprises dissolving the lignin, starch acetate, or combination thereofin a first solvent to provide a first solution; depositing the firstsolution on a plurality of fertilizer granules to form a first layer;dissolving the one or more second polymers in a second solvent toprovide a polymer solution; and depositing the polymer solution on thefirst layer-coated fertilizer granules to provide a second layer,optionally dissolving an additional second polymer in a third solvent toprovide an additional polymer solution; and depositing the additionalpolymer solution on the second layer-coated fertilizer granules toprovide a third layer.

Alternatively, a method of manufacture of the coated fertilizer of thesecond embodiment comprises dissolving the lignin, starch acetate, orcombination thereof in a first solvent to provide a first solution;depositing the lignin solution on a plurality of fertilizer granules toform a first layer; dissolving at least two second polymers in a solventto provide a second solution; and depositing the second solution on thefirst layer-coated fertilizer granules to provide the coated fertilizer.

A method of manufacture of the coated fertilizer of the secondembodiment also comprises contacting the lignin, starch acetate, or acombination thereof, and cellulose triacetate, poly(caprolactone), or acombination thereof in a solvent to provide a coating composition;depositing the coating composition on a plurality of fertilizer granulesto provide the coated fertilizer.

The above described and other features are further set forth in thefollowing figures, detailed description, and claims.

BRIEF DESCRIPTION OF THE FIGURES

The following figures are exemplary, and do not limit the claims.

FIG. 1 is a microscopic image of urea granules coated with 2 wt. % oflignin, 2 wt. % of cellulose acetate, and 0.5 wt. % of wax manufacturedby drip coating.

FIG. 2 is a microscopic image of urea granules coated with 2.5 wt. % oflignin, 3 wt. % of cellulose acetate, and 0.5 wt. % of wax manufacturedby spray coating.

FIG. 3 shows percent nitrogen release from urea granules coated with 3.0wt % of lignin, 3.0 wt. % of cellulose triacetate or cellulosetriacetate blends, and 1.5 wt % wax after 7 days at 100° F. (38° C.)This example is 7.5 wt % total coating, as the wax was not part of theblend, but added as a second layer.

FIG. 4 shows percent nitrogen release from urea granules coated with 3.0wt. % of cellulose triacetate or cellulose triacetate blends and 1.5%wax after 7 days at 100° F. (38° C.). This example is a 4.5 wt % totalcoating, as the wax was not part of the blend, but was added as a secondlayer.

FIG. 5 is a graph of percent nitrogen release after 3 days at 100° F.(38° C.) versus coating wt. % for urea granules coated withpoly(butylene succinate) (“PBS”) and wax and optionally lignin.

FIG. 6 is a graph of percent nitrogen release after 3 days at 100° F.(38° C.) versus coating wt. % for urea granules coated with poly(lacticacid) (“PLA”) and wax and optionally lignin.

FIG. 7 is a graph of percent nitrogen release after 7 days at 100° F.(38° C.) versus coating wt. % for urea granules coated with PBS/PLAcombinations and wax and optionally lignin.

FIG. 8 is a graph showing percent nitrogen release results vs. percentPLA at 100° F. (38° C.) of urea granules coated with PLA/PBScombinations at a 7.5 wt. % total coating level, wherein the coatingfurther includes wax and optionally lignin.

FIG. 9 is a graph showing percent nitrogen release vs. percent PLA andPBS after 7 days at 100° F. (38° C.) of urea granules coated with afirst lignin layer, a second layer of PBS (medium), PLA (high), or ablend of PBS (medium) and PLA (high), and a third wax layer.

FIG. 10 is a graph showing percent nitrogen release vs. percent PLA(high) and percent PBS (high) after 7 days at 100° F. (38° C.) of ureagranules coated with a first lignin layer, a second layer of PBS (high),PLA (high), or a blend of PBS (high) and PLA (high), and a third waxlayer.

FIG. 11 is a graph showing percent nitrogen release vs. percent PLA andpercent PBS after 7 days at 100° F. (38° C.) of urea granules coatedwith a first lignin layer, a second layer of PBS (high), and PLA (low),or a blend of PBS (high) and PLA (low), and a third wax layer.

FIG. 12 is a graph showing percent nitrogen release after 7 days at 100°F. (38° C.) of (a) urea granules coated with optionally a first ligninlayer, a second PBS layer, a third PLA layer, and a fourth wax layer;and (b) urea granules coated with a first lignin layer, a second PBS andPLA combination layer, and a third wax layer.

FIG. 13 is a graph of percent nitrogen release after 14 days at 100° F.(38° C.) of (a) urea granules coated with optionally a first ligninlayer, a second PBS layer, a third PLA layer, and a fourth wax layer;and (b) urea granules coated with a first lignin layer, a second PBS andPLA combination layer, and a third wax layer.

FIG. 14 is a graph showing percent nitrogen release after 7 days at 100°F. (38° C.) of urea granules coated with an optional first lignin layer,a second recycled PLA/PBS combination layer, and a third wax layer.

FIG. 15 is a graph showing percent nitrogen release after 14 days at100° F. (38° C.) of urea granules coated with an optional first ligninlayer, a second recycled PLA and PBS combination layer, and a third waxlayer.

FIG. 16 is a graph showing percent nitrogen release after 7 days at 100°F. (38° C.) of urea granules coated with a first optional lignin layer,a second recycled PLA and cellulose triacetate layer, and a third waxlayer.

FIG. 17 is a graph showing percent nitrogen release after 14 days at100° F. (38° C.) of urea granules coated with a first optional ligninlayer, a second recycled PLA and cellulose triacetate combination layer,and a third wax layer.

DETAILED DESCRIPTION

The inventors hereof have developed fertilizer coatings comprisingvarious combinations of one or more of poly(lactic acid), poly(butylenesuccinate), cellulose triacetate, lignin, and wax. The fertilizercoatings are biodegradable, and leave no toxic residues in the soil.Fertilizers coated with such coatings further have sustainable nutrientrelease rates, matching or approaching nutrient uptake rate of mostplant, thus improving the yields. Further, the granule coating methodsdescribed herein allow the manufacture of coated fertilizers having aneven and thin coating, which allows coated fertilizers to contain highnitrogen contents.

The coatings are compatible with a wide variety of fertilizer granules.The fertilizer granules can comprise nitrogen, phosphorus, or potassiumsources such as ammonium nitrate, ammonium sulfate, ammonium sulfatenitrate, calcium nitrate, calcium ammonium nitrate, urea,urea-formaldehyde, monoammonium phosphate (“MAP”), diammonium phosphate,polyphosphate compounds, phosphate rock, single superphosphate (“SSP”),triple super phosphate, potassium nitrate, potassium chloride, orpotassium sulfate (“SOP” or potash). Combinations comprising theforegoing may also be used. In an embodiment, the fertilizer granulescomprise urea. The amounts of nitrogen, phosphorus, or potassium sourcesincluded in the final fertilizer granules depends on the intended enduse, and can be 0 to 60 wt. % for each component, based on the totalweight of the fertilizer granule.

Additionally magnesium sulfate and a source of one or more traceelements, i.e., micronutrients can be included, for example boron,calcium, chlorine, cobalt, copper, iron, manganese, molybdenum, nickel,sodium, zinc, or a combination comprising at least one of the foregoingcan be present. These nutrients may be supplied in elemental form or inthe form of salts, for examples as sulfates, nitrates, or halides. Theamount of plant micronutrients depends on the intended end use and canbe, for example, 0.1 to 5 wt. %, based on the total weight of thefertilizer granule.

Fillers can further be present in the granule, for example bentonite,calcite, calcium oxide, calcium sulfate (anhydrous or hemihydrate),dolomite, talc, sand, or a combination comprising at least one of theforegoing fillers.

Other components of granular fertilizers can include, for example,surfactants (if a liquid is present as described below), nucleationagents, or recycled fertilizer particles, which can act as a source ofagents, nucleating soil conditioners such as calcium carbonate,activated carbon, elemental sulfur, biocides such as pesticides,herbicides, or fungicides, wicking agents, wetting agents, heatstabilizers, adhesives such as cellulose, polyvinyl alcohols, fats,oils, gum arabics, vinylidene ultraviolet stabilizers, antioxidants,reducing agents, colorants, binders (i.e., organochlorides, zeins,gelatins, chitosan, polyethylene oxide polymers, and acrylamide polymersand copolymers), and the like.

The fertilizer granules can have any shape or size suitable for theirintended use. In an embodiment the fertilizer granules are substantiallyspherical. The fertilizer granules have an average particle diameter of1.0 to 4.0 millimeters (mm). Within this range the average particlediameter can be greater than or equal to 1.5, or greater than or equalto 2.0 mm. Also within this range the average particle diameter can beless than or equal to 3.5, or less than or equal to 3.0 mm. In anembodiment at least 90% by weight of the fertilizer granules have aparticle diameter of 2.0 to 4.0 mm. Particle diameter is determinedaccording to “Size Analysis—Sieve Method” IFDC S-107 issued byInternational Fertilizer Development Center (IFDC) which is the mostcommon and internationally approved method used to determine fertilizerparticle size.

In an embodiment, the coating on the fertilizer granule comprises atleast three components: a poly(lactic acid), a second polymer, which ispoly(butylene succinate), cellulose triacetate, or a combinationthereof, and a sealant. For example, the coating comprises poly(lacticacid), poly(butylene succinate), and a sealant. Alternatively, thecoating comprises poly(lactic acid), cellulose triacetate, and asealant. In these embodiments, no lignin is present in the coatings.

The poly(lactic acid) can have a weight average molecular weight (M_(w))of 50,000 to 250,000 g/mol. As used herein, PLA (high) can refer topoly(lactic acid) having an M_(w) of 150000 to 210000 g/mol,specifically 175000 to 190000 g/mol. PLA (low) refers to poly(lacticacid) having an M_(w) of 30000 to 70000 g/mol, specifically 40000 to65000 g/mol.

The recycled poly(lactic acid) can have a weight average molecularweight (M_(w)) of 30,000 to 250,000 g/mol, more specifically 100,000 to200 000 g/mol.

The poly(butylene adipate-co-terephthalate) (Ecoflex) can have a weightaverage molecular weight (M_(w)) of 30,000 to 120,000 g/mol, morespecifically 50,000 to 100000 g/mol.

The cellulose acetate can have a weight average molecular weight (M_(w))of 25,000 to 120,000 g/mol, more specifically 35000 to 70000 g/mol

The poly(butylene succinate) can have an M_(w) of 70,000 to 160,000g/mol. As used herein, PBS (high) can refer to poly(butylene succinate)having an M_(w) of 100,000 to 150000 g/mol, specifically 120000 to140000 g/mol. PBS (medium) refers to poly(butylene succinate) having anM_(w) of 75000 to 125000 g/mol, specifically 90000 to 110000 g/mol.

The cellulose triacetate can have an M_(w) of 100,000 to 350,000 g/mol,specifically 12,5000 to 300,000 g/mol, more specifically 200,000 to275,000 g/mol. The weight ratio of the poly(lactic acid) to the secondpolymer can be 10:1 to 1:10, for example, 5:1 to 1:5, 3:1 to 1:3, or 2:1to 1:2.

The sealant further protects the granules from abrasion and moistureduring shipping and storage, and comprises a wax. Waxes are liquid at110 to 200° F. (43 to 95° C.). Examples of waxes include naturalpetroleum waxes, including paraffin waxes (hard, crystalline, brittlewaxes composed primarily of unbranched alkanes, typically having meltingpoints from 118 to 158° F. (48 to 70° C.), and microcrystalline waxes(soft, amorphous, malleable waxes composed primarily of branchedalkanes, typically having melting points from 129 to 203° F. (54 to 95°C.), and fully refined paraffin waxes). Synthetic waxes can also beused, including polyethylene waxes having, for example a degree ofpolymerization of 10 to 18 carbon atoms. Exemplary waxes that arecommercially available include a petroleum wax, C30+ from ChevronPhillips Chemical (CP-Chem), 7089A, R-4408, and R-3053A available fromInternational Group, Inc. The wax can be present in the coating in anamount effective to provide 0.1 to 3 wt. %, 0.2 to 2 wt. %, or 0.5 to1.8 wt. % of wax, based on the total weight of the coated fertilizer.

The coating can accordingly comprise more than 0, e.g., 0.1 to 5.7 wt. %of poly(lactic acid), 0.1 to 5.7 wt. % of the second polymer, and 0.1 to3 wt. % of the sealant. In another embodiment, the coating can comprise0.5 to 4.8 wt. % of poly(lactic acid), 0.5 to 4.8 wt. % of the secondpolymer, and 0.2 to 2 wt. % of the sealant.

When coated on the fertilizer granules, the amount of the coating(including the poly(lactic acid), the second polymer, and a sealant) isless than or equal to 6 wt. %, for example, 0.1 to 6 wt. %, 0.5 to 5 wt.%, 2 to 5 wt. %, or 3 to 5 wt. %, based on the total weight of thecoated fertilizer.

The components of the coating are present in more than one layer. Forexample, in an embodiment, the coated fertilizer comprises a first layerdisposed on the fertilizer granule, wherein the first layer comprisesthe poly(lactic acid) and the second polymer; and a second layerdisposed on the first layer, wherein the second layer comprises thesealant. In another embodiment, the coated fertilizer comprises threelayers wherein the first layer is disposed on the fertilizer granule,the second layer is disposed on the first layer, and the third layer isdisposed on the second layer. The first layer can comprise poly(lacticacid) or the second polymer. The second layer can also comprisepoly(lactic acid) or the second polymer, provided that the material inthe first layer is not the same as the material in the second layer. Thethird layer can comprise the sealant.

In another embodiment, the coating comprises a first polymer comprisinglignin, starch acetate, or a combination thereof, and a second polymer,where the second polymer can be poly(lactic acid), poly(butylenesuccinate), cellulose triacetate, poly(caprolactone), poly(butyleneterephthalate adipate), cellulose acetate, or a combination comprisingat least one of the foregoing.

Lignin is a polymer of aromatic alcohols most commonly derived fromwood. Lignin can be obtained by the Kraft process. Exemplary ligninincludes Kraft lignin marketed under the name of Indulin* AT orProtobind* 1000.

Starch acetate is a starch that has been acetylated to a degree ofsubstitution (DS) of 1 to 3 with an acetyl value of 20% to 70%. As usedherein, “acetyl value” refers to the weight percent (wt %) of aceticacid per unit measure of starch acetate. For example, an acetyl value ofapproximately 62.5 is equivalent to a DS of 3.0.

The second polymer includes poly(lactic acid), poly(butylene succinate),and cellulose triacetate as described above, as well aspoly(caprolactone), poly(butylene terephthalate adipate), and celluloseacetate. The foregoing polymers can have an Mw in the range of 8,000 to500,000 g/mol.

The weight ratio of the lignin, starch acetate, or a combination thereofto the second polymer can be 1:10 to 10:1, 5:1 to 1:5, 3:1 to 1:3, or2:1 to 1:2. Lignin, the starch acetate, or the combination thereof ispresent in an amount of 0.1 wt. % to 6 wt. %, 0.1 wt. % to 5 wt. %, 0.1wt. % to 3.5 wt. %, 0.2 wt. % to 3 wt. %, or 0.5 to 3 wt. %, based onthe total weight of the coated fertilizer.

Optionally, the coating comprising the lignin, the starch acetate, or acombination thereof and the second polymer further comprises a sealantas described above. The sealant can be present in an amount of 0 to 5wt. %, 0 to 3 wt. %, 0.1 to 3 wt. %, 0.2 to 2 wt. %, 0.1 to 1 wt. %, or0.5 to 1.8 wt. %, based on the total weight of the coated fertilizer.

The coating can accordingly comprise more than 0, e.g., 0.1 to 5 wt. %of lignin, starch acetate, or a combination thereof, 0.1 to 6 wt. % ofthe second polymer, and 0 to 5 wt. % of the sealant. In anotherembodiment, the coating can comprise 0.1 to 6 wt. % of lignin, starchacetate, or a combination thereof 0.1 to 5 wt. % of the second polymer,and 0 to 3 wt. % of the sealant. Preferably the coating comprises 0.2 to3 wt. % of lignin or starch acetate, 0.2 to 3 wt. % of the secondpolymer, and 0 to 1 wt. % of the sealant.

When coated on the fertilizer granules, the amount of the coating(lignin, starch acetate, or a combination thereof, second polymer, andoptional sealant) is 0.5 wt. % to 10 wt. %, 1 wt. % to 9 wt. %, 2 wt. %to 8 wt. %, 2 wt. % to 7 wt. %, 2 wt. % to 6 wt. %, or 2 wt. % to 5 wt.%, based on the total weight of the coated fertilizer.

The components of the coating can be present in more than one layer. Forexample, in an embodiment, the coated fertilizer comprises a first layerdisposed on the fertilizer granule, wherein the first layer comprisesthe lignin, starch acetate, or a combination thereof; and a second layerdisposed on the first layer, wherein the second layer comprises thesecond polymer. Optionally the sealant can be present in a third layerdisposed on the second layer.

In any of the foregoing embodiments, the coatings can further comprisean adjuvant as known in the art, for example a colorant, an adhesionpromoter, or a surfactant, provided that the adjuvant does notsignificantly adversely affect the desired properties of the coatedfertilizer. For example, a surfactant can include a primary andsecondary (C₁₆₋₃₀)alkylamine, a (C₁₆₋₃₀)fatty acid amide of a primary(C₁₆₋₃₀)alkylamine, or a (C₁₆₋₃₀)fatty acid ester of a (C₁₆₋₃₀)alkanol.Examples of the foregoing surfactants include cetyl amine, stearylamine, arachidyl amine, behenyl amine, dicetyl amine, distearyl amine,diarachidyl amine, dibehenyl amine, di(hydrogenated tallow) amine, cetylstearamide, stearyl stearamide, stearyl erucamide, erucyl erucamide,candililla wax, carnauba wax, and montan wax.

Further in any of the foregoing embodiments, the coating or individuallayers are disposed directly on the granule or other layers, that is, nointervening layers are present other than those described. The coatingsand layers can be continuous or discontinuous. To optimize the sustainedrelease features of the coated fertilizer the coating covers 90 to 100%of the surface area of the fertilizer granule. For coatings having morethan one layer, each layer covers 90 to 100% of the surface area of thefertilizer granule or the underlying layer.

The thickness of the coating is adjusted to provide the desiredsustained release and protection properties. In an embodiment, the totalthickness of the coating is 20 to 70 micrometers. Within this range thethickness may be greater than or equal to 25, or greater than or equalto 30 micrometers. Also within this range the thickness may be less thanor equal to 65, or less than or equal to 60 micrometers.

The coated fertilizer can be manufactured by various methods. Thefertilizer granules can be coated by spray coating (for example, top,bottom, or side spray coating), drum coating, pan coating, fluid bedcoating, continuous pour coating, or any other method known to those ofskill in the art. This coating can be done in a batch or in a continuousprocess. The granules can be coated with a single layer in a singlecoating application, or the granules can be coated with multiple layersof the same coating material, such as, 2, 3, 4, 5, or more layers. Whencoating the core, the coating composition, e.g., the sealant, can beheated to above its melting point temperature so that the coatingmaterial is in a liquid state when it is applied to the core. Afterapplication of the liquid coating material to the core, the coated coreis allowed to cool so that the coating material solidifies forming asolid layer surrounding the core. This process may be repeated one ormore times to produce multiple layers of the same or different coatingmaterials surrounding the core. Alternatively, the coating material canbe dissolved or suspended in a solvent, applied to the granules, and thesolvent evaporated. This process may be repeated one or more times toproduce multiple layers of the same or different coating materialssurrounding the core.

In a specific embodiment, a method of manufacturing a coated fertilizercomprises dissolving poly(lactic acid) and a second polymer selectedfrom poly(butylene succinate), cellulose triacetate, or a combinationthereof in a solvent to provide a polymer solution; spraying the polymersolution onto a plurality of fertilizer granules to form a first layer;and coating a sealant on the first layer to provide a second layerdeposited on the first layer. The sealant can be coated by, for example,melt coating techniques. The solvent used to dissolve the poly(lacticacid) and the second polymer can be dichloromethane To facilitate theformation of the polymer solution, the polymers and the solvent can bemixed at an elevated temperature where the solids content of thesolution can be 5 to 15% of the composition by weight.

When the coating comprises lignin, starch acetate, or combinationthereof, to form a coated fertilizer, sequential coating or simultaneouscoating methods can be used. An example of a sequential coating methodcomprises dissolving the lignin, starch acetate, or combination thereofin a first solvent to form a first solution; depositing, e.g., sprayingthe first solution onto a plurality of fertilizer granules to form afirst, lignin or starch acetate layer; dissolving the second polymer ina second solvent to provide a polymer solution; and depositing, e.g.,spraying the second polymer solution on the first, lignin or starchacetate layer to form a second polymer layer deposited on the firstlayer. Optionally, at least two different second polymers can be presentin the second solution. In another embodiment, an additional secondpolymer (different from the second polymer(s) of the second layer) canbe dissolved in a third solvent, and deposited, e.g., by spraying on thesecond layer to form a third layer deposited on the second layer. Thesecond layer or the third layer, when present, can optionally be furthercoated with a sealant to provide a sealant layer deposited on the secondor third layer.

The solvent used to dissolve lignin, starch acetate, or combinationthereof can comprise acetone and water having a volume ratio of 70:30 to90:10, for example, 80:20 to 90:10. When the second polymer comprisescellulose triacetate, poly(caprolactone), or a combination thereof, thesolvent used to dissolve the polymer can comprise acetone or acombination of acetone and water having a volume ratio of 70:30 to90:10. When the second polymer comprises poly(lactic acid),poly(butylene succinate), poly (butylene terephthalate adipate),cellulose acetate, or a combination thereof, the solvent used todissolve the polymer can comprise dichloromethane To facilitate theformation of the lignin/starch acetate first solution or the polymersolution, the polymers and the solvent can be mixed at an elevatedtemperature. The solids content of the lignin/starch acetate solutionand the polymer solution can be 5 to 15% of the composition by weight.

A simultaneous coating method comprises dissolving the lignin, starchacetate, or combination thereof and the second polymer in a solvent toprovide a coating composition. The second polymer is accordinglyselected to be soluble in the same solvent as the lignin, starchacetate, or combination thereof, for example, cellulose triacetate,poly(caprolactone), or a combination thereof. The coating composition isdeposited, e.g., by spraying the coating composition onto a plurality ofthe fertilizer granules to provide a first layer. The method optionallyfurther comprises coating with a sealant to provide a second layer. Thesealant can be coated by melt coating techniques.

In use, the coated fertilizer is applied to the locus of a plant orseed, in particular the soil of a plant or seed to be fertilized.

The fertilizer coatings are biodegradable, and leave no toxic residuesin the soil. Fertilizers coated with such coatings further havesustainable nutrient release rates. Further, the granule coating methodsdescribed herein allow the manufacture of coated fertilizers having aneven and thin coating, which allows coated fertilizers to contain a highnitrogen content. For example, when the fertilizer is urea, the nitrogencontent of the coated fertilizer is 42 wt. % to 45 wt. %. Fertilizercoatings containing lignin can suppress NOx production.

The coated fertilizers having sustained release properties are furtherillustrated by the following non-limiting examples.

The methods disclosed herein can, in some aspects, be performed on anindustrial scale.

ASPECTS

Disclosed herein are at least the following aspects:

Aspect 1: A coated fertilizer comprising:

a fertilizer granule; and

a coating disposed on a surface of the fertilizer granule, wherein thecoating comprises

-   -   a poly(lactic acid);    -   a second polymer comprising a poly(butylene succinate), a        cellulose triacetate,

or a combination comprising at least one of the foregoing; and

-   -   a sealant.

Aspect 2: The coated fertilizer of claim 1, wherein the sealantcomprises a wax.

Aspect 3: The coated fertilizer of claim 1 or 2, wherein the secondpolymer comprises poly(butylene succinate).

Aspect 4: The coated fertilizer of any one of claims 1 to 3, wherein thesecond polymer comprises cellulose triacetate.

Aspect 5: The coated fertilizer of any one of claims 1 to 4, wherein aweight ratio of the poly(lactic acid) to the second polymer is 10:1 to1:10.

Aspect 6: The coated fertilizer of any one of claims 1 to 5, wherein anamount of the coating is 0.5 wt. % to 6 wt. %, based on the total weightof the coated fertilizer.

Aspect 7: The coated fertilizer of any one of claims 1 to 6, wherein thenitrogen content of the coated fertilizer is 42 wt. % to 45 wt. %, basedon the total weight of the coated fertilizer.

Aspect 8: The coated fertilizer of any one of claims 1 to 7, wherein thecoating comprises the poly(lactic acid), the second polymer, and thesealant in combination in a single layer.

Aspect 9: The coated fertilizer of any one of claims 1 to 7, wherein thecoating comprises:

-   -   a first layer disposed on the fertilizer granule, wherein the        first layer comprises the poly(lactic acid) and the second        polymer; and    -   a second layer disposed on the first layer, wherein the second        layer comprises the sealant.

Aspect 10: The coated fertilizer of any one of claims 1 to 7, whereinthe coating comprises:

a first layer disposed on the fertilizer granule, wherein the firstlayer comprises the poly(lactic acid) or the second polymer;

a second layer disposed on the first layer, wherein the second layercomprises the second polymer or the poly(lactic acid), provided that thefirst layer is not the same as the second layer; and

a third layer disposed on the second layer, wherein the third layercomprises the sealant.

Aspect 11: The coated fertilizer of any one of claims 1 to 10, whereinthe coating has a total thickness of 20 to 70 micrometers.

Aspect 12: A method of manufacture of the coated fertilizer any one ofclaims 1 to 11, the method comprising:

combining the poly(lactic acid), the second polymer, and the sealant toprovide a coating composition; and

depositing the coating composition as a layer on a plurality offertilizer granules to provide the coated fertilizer.

Aspect 13: The method of claim 12, wherein the depositing comprisesspraying the coating composition.

Aspect 14: A method of making the coated fertilizer of any one of claims1 to 11, the method comprising:

dissolving the poly(lactic acid) and the second polymer in a solvent toprovide a solution;

depositing the solution on a fertilizer granule to form a first layer;and

depositing a sealant on the first layer-coated fertilizer granules toform a second layer.

Aspect 15: A coated fertilizer comprising:

a fertilizer granule; and

a coating disposed on the fertilizer granule, wherein the coatingcomprises

-   -   lignin, starch acetate, or a combination thereof; and    -   a second polymer comprising a poly(lactic acid), a poly(butylene        succinate), a

cellulose triacetate, a poly(caprolactone), a poly(butyleneterephthalate adipate), a

cellulose acetate, or a combination comprising at least one of theforegoing.

Aspect 16: The coated fertilizer of claim 15, wherein the coatingfurther comprises a sealant.

Aspect 17: The coated fertilizer of claim 16, wherein the sealantcomprises a wax.

Aspect 18: The coated fertilizer of any one of claims 15 to 17, whereinan amount of the coating is 0.5 wt. % to 10 wt. %, based on the totalweight of the coated fertilizer.

Aspect 19: The coated fertilizer of any one of claims 15 to 18, whereinthe weight ratio of the lignin, starch acetate, or a combination thereofto the second polymer is 1:10 to 10:1.

Aspect 20: The coated fertilizer of any one of claims 15 to 19, whereinthe second polymer comprises a combination of poly(lactic acid) andpoly(butylene succinate).

Aspect 21: The coated fertilizer of any one of claims 15 to 20, whereinthe coating comprises:

a first layer disposed on the fertilizer granule, wherein the firstlayer comprises the lignin, starch acetate, or a combination thereof;

a second layer disposed on the first layer, wherein the second layercomprises one or more second polymers; and

optionally, a third layer, wherein the third layer comprises anadditional second polymer.

Aspect 22: The coated fertilizer of claim 21, wherein the coatingfurther comprises a sealant layer disposed on the second layer or thirdlayer, wherein the sealant layer comprises a sealant.

Aspect 23: The coated fertilizer of claim 21, wherein the second layercomprises poly(butylene succinate); and the third layer is present, andcomprises poly(lactic acid).

Aspect 24: A method of making the coated fertilizer of claim 21, themethod comprising dissolving the lignin, starch acetate, or acombination thereof in a first solvent to provide a first solution;depositing the first solution on a plurality of fertilizer granules toform a first layer; dissolving the one or more second polymers in asecond solvent to provide a polymer solution; depositing the polymersolution on the first layer-coated fertilizer granules to provide asecond layer; optionally dissolving an additional second polymer in athird solvent to provide an additional polymer solution; and depositingthe additional polymer solution on the second layer-coated fertilizergranules to provide a third layer.

Aspect 25: The method of claim 24, further comprising depositing asealant on the second layer-coated fertilizer granules or the thirdlayer-coated fertilizer granules.

Aspect 26: The method of claim 24, wherein the depositing comprisesspraying the coating composition.

Aspect 27: The method of any one of claims 24 to 26, wherein the secondpolymer comprises poly(lactic acid), poly(butylene succinate), poly(butylene terephthalate adipate), cellulose acetate, or a combinationthereof, and the second solvent comprises dichloromethane

Aspect 28: A method of manufacture of the coated fertilizer of claim 21,the method comprising: dissolving the lignin, starch acetate, or acombination thereof in a first solvent to provide a first solution;depositing the first solution on a plurality of fertilizer granules toform a first layer; dissolving at least two second polymers in a solventto provide a second solution; and depositing the second solution on thefirst layer-coated fertilizer granules to provide the coated fertilizer.

Aspect 29: The method of claim 28, further comprising depositing asealant on the coated fertilizer.

Aspect 30: The method of claim 28 or 29, wherein the at least two secondpolymers comprise two of poly(lactic acid), poly(butylene succinate),poly (butylene terephthalate adipate), cellulose acetate; and the secondsolvent comprises dichloromethane

Aspect 31: A method of manufacture of the coated fertilizer of claim 21,the method comprising contacting the lignin, starch acetate, orcombination thereof, and cellulose triacetate, poly(caprolactone), or acombination thereof in a solvent to provide a coating composition;depositing the coating composition on a plurality of fertilizer granulesto provide the coated fertilizer.

Aspect 32: The method of claim 31, further comprising depositing asealant on the coated fertilizer.

EXAMPLES

The materials used in the Examples are described in Table 1.

TABLE 1 Component Chemical Description Source CA (high) Celluloseacetate (Grade no.) Eastman CA (low) Cellulose acetate (Grade no.)Eastman CTA Cellulose triacetate Fischer Scientific Lignin-1 HydrophobicKraft lignin, Asian Lignin protobind* 1000 Ltd Lignin-2 HydrophobicKraft lignin, Meadwestwaco Indulin* AT PBS (high) Poly(butylenesuccinate) Danimer PBS (medium) Poly(butylene succinate) Danimer PLA(high) Poly(lactic acid) Natureworks PLA (low) Poly(lactic acid)Natureworks PLA Repro-pkg Recycled poly(lactic acid) Phoenix recyclingPLA Repro-box Recycled poly(lactic acid) Phoenix recycling PLARepro-label Recycled poly(lactic acid) Phoenix recycling PLA 2500 HPRecycled poly(lactic acid), Natureworks high crystalline grade of PLAPLA 3100 HP Recycled poly(lactic acid), Natureworks high crystallinegrade of PLA PBAT Poly(butylene terephthalate BASF adipate) (Ecoflex*)C30+ Alpha-olefin wax CP-Chem 7089A Petroleum wax, congealing point,International 148 F. (64° C.) Group, Inc. R-4408A Wax, drop melt point,165 F. International (74° C.) Group, Inc. R-3053A Petroleum wax,congealing point, International 164 F. (73° C.) Group, Inc. AcetoneAldrich Dichloromethane Aldrich

General Procedures

Preparation of coating formulations. Lignin solution was made usingacetone-water solvent mixtures in ratios from 80:20 to 90:10 at roomtemperature with stirring for 12 hours. CA solutions were made usingacetone solvent at 60° C. with gentle stirring at 100 RPM for 60 minutesuntil complete dissolution was observed. PBS (at 40° C.), PLA (at roomtemperature), CTA (at 40° C.), PBAT (at 40° C.) as well as theirrespective blend solutions (at 40° C.) were made using dichloromethanesolvent with gentle stirring at 100 revolutions per minute (rpm) for 60minutes until complete dissolution was observed.

Coating procedure. Except in the case of drip coating experiments forCA, both polymer and lignin solutions were coated using an air atomizedspray onto the urea granules placed in a rotating drum. Experimentswhere lignin, polymer, and wax were all used, for a sequential coatingprocess, lignin was coated first followed by a polymer or a polymerblend and finally melt coating of wax; and for a simultaneous process, ablend of lignin and a polymer or a polymer blend was coated firstfollowed by melt coating of wax.

Accelerated nutrient release test. The test is used to mimic a releaseprofile of nutrient at given time intervals. The time intervals thatsamples were taken and analyzed were 2 hours, 4 hours, and 24 hours. A5% dilute citric acid solution in water was recirculated across a bed ofproduct granules and the filtrate was analyzed for nitrogen content. Thecitric acid simulates the soil conditions that a product would besubjected to during normal application.

Three, seven, and 14 day oven test. A container was charged with 100 gof sample and 500 mL of water. The container was then sealed and placedin an over at 100° F. (38° C.). Nitrogen release was measuredperiodically after 3 days, 7 days, or 14 days.

Comparative Example A Drip Coating

Coating formulations were added dropwise to urea granules in a rotarydrum. An air blower was used in the drum to remove the solvent vapors.For coatings containing both CA and lignin, the urea was first coated bylignin followed by CA. The addition of wax sealant was also performed asthe final coating by melting the wax and pouring the melted wax into therotating drum containing polymer (and/or lignin) coated urea. In theseexperiments, the lignin percentage was varied from 0 to 3%, CA wasvaried between 0 to 6%, and the sealant was varied between 0 to 1.5%.

None of the samples coated by the drip process led to uniform coatingFurther measurements were not carried out. FIG. 1 shows a representativeexample of a sample coated with 2% lignin, 2% CA, and 0.5% IGI-7089Awith drip coating. Coating defects such as dark and light contrast wereobserved. These defects indicate unevenness of the coating.Agglomeration of the granules was also observed.

Comparative Examples 1-25 and Example 26 Cellulose Acetate with/withoutLignin

Coating formulations were sprayed onto urea granules. The total coatingwas varied between 5.5 and 7.5 wt. %. Wax was varied between 0.5 and 1.5wt. %. Lignin was varied between 0 and 3 wt. %, and CA was variedbetween 3 and 6 wt. %. The coating formulations and the acceleratednutrient release test results are shown in Table 2. The coated sample ofexample 1 was also shown in FIG. 2. No major coating defects wereobserved.

TABLE 2 Accelerated release Lignin/CA/wax Total coating CA Sealant test(% N release) Ex. (wt. %) (wt. %) Lignin Type Type Type N (wt. %) 2 hr 4hr 24 hr 1 2.5/3/0.5 6 Lignin-1 High 7089A 43.99 6.13 25.96 97.4 22/3/0.5 5.5 Lignin-1 High 7089A 43.75 *** *** *** 3 2/3/1 6 Lignin-1High 7089A 44.34 *** *** *** 4 2.5/3/0.5 6 Lignin-1 High 7089A 44.254.11 12.48 100.00 5 2.5/3/1 6.5 Lignin-1 High 7089A 44.00 1.62 4.29100.00 6 2.5/3/0.5 6 Lignin-2 High 7089A 44.14 1.65 9.39 100.00 72.5/3/1 6.5 Lignin-2 High 7089A 44.19 2.57 7.76 100.00 8 3/3/0.5 6.5Lignin-1 High 7089A 43.77 3.95 11.54 100.00 9 3/3/1 7 Lignin-1 High7089A 43.18 1.06 3.54 100.00 10 2/4/0.5 6.5 Lignin-1 High 7089A 43.513.56 9.45 99.55 11 2/4/1 7 Lignin-1 High 7089A 43.23 2.47 9.02 100.00 120/6/0.5 6.5 *** High 7089A 43.40 6.46 22.15 100.00 13 0/6/1 7 *** High7089A 43.48 3.27 14.44 100.00 14 3/3/0.5 6.5 Lignin-1 High 7089A 43.51*** *** *** 15 3/3/1 7 Lignin-1 High 7089A 43.52 2.04 5.69 91.43 162/4/0.5 6.5 Lignin-1 Low 7089A 43.30 *** *** *** 17 2/4/1 7 Lignin-1 Low7089A 43.66 1.47 6.5 92.08 18 3/3/0.5 6.5 Lignin-1 Low 7089A 43.52 ****** *** 19 3/3/1 7 Lignin-1 Low 7089A 42.98 *** *** *** 20 2/4/0.5 6.5Lignin-1 Low 7089A 43.47 *** *** *** 21 2/4/1 7 Lignin-1 Low 7089A 42.83*** *** *** 22 0/5/1.5 6.5 *** Low R-4408A 43.74 *** *** *** 23 0/5/1.56.5 *** Low R-3053A 43.57 *** *** *** 24 3/3/1.5 7.5 Lignin-1 LowR-4408A 43.46 1.99 36.37 96.64 25 3/3/1.5 7.5 Lignin-1 Low R-3053A 43.483.56 9.16 95.25 26 3/3/1.5 7.5 Lignin-1 High C30+ 43.79 2.64 39.69 74.07*** Sample was observed to leak when placed in water under an opticalmicroscope. Accordingly, the samples were not tested.

As can be seen from the data in Table 2, a combination of lignin,cellulose acetate, and a wax sealant (Example 26) was most effective todelay nitrogen release.

Comparative Examples 27-36 Cellulose Triacetate with/without Lignin

Granular urea was coated with various cellulose triacetate coatingsystems. In these experiments, the lignin percentage was varied between0 and 3 wt. %, CTA or CTA-PBS or CTA-PLA was constant at 3 wt. % and thesealant was constant at 1.5 wt. %. If present, lignin-1 was used. Thecoating formulations and the nitrogen release test results are shown inTable 3. The seven day release results are also illustrated graphicallyin FIGS. 3 and 4.

TABLE 3 Accelerated Nutrient 7-Day Release L/CTA/PBS/PLA/W* PolymerCoating Sealant Sealant N Release Test, % test, % (Oven) Ex. (wt. %)Type (wt. %) Type (wt. %) (wt. %) 2 hr 4 hr 24 hr 3 Day 7 Day 273/3/0/0/1.5 CTA 7.5 R- 1.5 43.55 1.1 5.41 70.28 62.34 88.91 3053A 283/1.5/1.5/0/1.5 PBS (high) 7.5 R- 1.5 43.35 1.69 3.03 27.16 16.37 37.673053A 29 3/1.5/1.5/0/1.5 PBS (med) 7.5 R- 1.5 43.12 1.29 2.07 13.94 15.522.74 3053A 30 3/1.5/0/1.5/1.5 PLA (high) 7.5 R- 1.5 43.22 0.56 0.9 5.451.3 8.73 3053A 31 3/1.5/0/1.5/1.5 PLA(low) 7.5 R- 1.5 43.24 0.33 0.44.42 0.19 3.85 3053A 32 0/3/0/0/1.5 CTA 4.5 R- 1.5 44.16 2.56 33.3593.27 91.94 95.39 3053A 33 0/1.5/1.5/0/1.5 PBS(high) 4.5 R- 1.5 44.3117.62 26.53 61.48 51.49 75.74 3053A 34 0/1.5/1.5/0/1.5 PBS (med) 4.5 R-1.5 44.48 6.03 9.78 56.58 29.32 66.93 3053A 35 0/1.5/0/1.5/1.5 PLA(high) 4.5 R- 1.5 44.42 0.75 1.44 11.99 3.8 12.36 3053A 360/1.5/0/1.5/1.5 PLA (low) 4.5 R- 1.5 44.2 0.14 0.43 24.54 0.94 23.23053A *“L” refers to lignin and “W” refers to wax.

FIG. 3 shows that at the 7.5 wt. % coating level, the lignin/CTA/waxcoating performance was inferior to the lignin/PBS/CTA/wax in retainingurea based on the 7 day oven test. FIG. 4 shows that at 4.5 wt. %coating level, PLA/CTA blends performed better than PBS/CTA blends inretaining urea based on the 7 day oven test. The data also indicatesthat the release performance was improved with the addition of a ligninprecoat.

Comparative Examples 37-40 PBAT with/without Lignin

Granular urea was coated with various PBAT systems with or withoutlignin. If present, lignin-1 was used. In these examples, the ligninpercentage was varied between 0 and 3 wt. %. PBAT was varied between 3and 5 wt. % and the sealant was kept constant at 1.5 wt. %. The totalcoating was varied between 6.5 wt. % and 7.5 wt. %. The coatingformulations and the nitrogen release test results are shown in Table 4.

TABLE 4 Accelerated 7-Day Nutrient Release Release test, % L/P/W*Coating Sealant Test, % (Oven Test) Ex. (wt. %) (wt. %) Type N (wt. %) 2hr 4 hr 24 hr 3 Day 7 Day 37 3/3/1.5 7.5 R- 42.68 6.57 16.71 74.67 88.2695.77 3053A 38 3/3/1.5 7.5 C30+ 42.74 6.45 22.03 80.16 98.13 99.80 390/5/1.5 6.5 R- 44.02 70.40 93.68 100 92.61 95.82 3053A 40 0/5/1.5 6.5C30+ 43.52 13.79 25.66 93.97 55.15 89.69 *“L” refers to lignin, “P”refers to “polymer” and “W” refers to wax.

Spray coating of lignin and PBAT followed by wax coating showed positiveresults based on 4 hr accelerated test data. However, 3 day and 7 dayrelease tests at 100° F. (38° C.) performed less than desirably.

Examples 41-81 PBS with/without Lignin

In these examples, the total coating was varied between 2.2 to 7.5 wt.%. Lignin (lignin-1, L) was varied between 0 and 3 wt. %, PBS (P) wasvaried between 1.2 to 4 wt. %, and the sealant (W) was varied between0.5 and 1.5 wt. %. The coating formulations and the nitrogen releasetest results are shown in Table 5.

TABLE 5 Accelerated Nutrient 7-Day (Oven L/P/W* PBS Total coatingSealant N Release Test, % Test), % Ex. (wt. %) Type (wt. %) Type (wt. %)2 hr 4 hr 24 hr 3 Day 7 Day 41 3/3/1.5 High 7.5 R-3053A 42.86 0.58 2.3320.42 22.09 37.98 42 2/3/1.5 High 6.5 C30+ 43.61 0.18 0.37 54.41 26.87*** 43 0/3/1.5 High 4.5 C30+ 44.29 1.23 19.14 51.05 16.96 60.26 440/2/1.5 High 3.5 C30+ 44.85 2.19 5.1 57.63 24.76 63.99 45 3/3/1.5 Medium7.5 C30+ 43.37 0.39 6.69 57.39 21.83 76.31 46 3/3/1.5 Medium 7.5 R-3053A42.99 0.38 0.64 7.84 5.75 13.42 47 2/3/1.5 Medium 6.5 C30+ 43.29 0.261.39 82.96 18.13 71.5 48 0/3/1.5 Medium 4.5 C30+ 44.26 0.26 0.77 68.823.54 34.46 49 0/4/1.5 Medium 5.5 C30+ 43.97 1.19 1.68 24.65 8.21 41.5950 0/3/1.5 Medium 4.5 R-3053A 44.32 7.85 13.96 32.66 25.27 53.19 513/3/1.5 High 7.5 C30+ 43.33 1.09 3.28 56.59 35.23 79.93 52 3/1.5/1.5High 6 C30+ 43.64 0.08 3.17 55.58 38.13 81.39 53 2/2/1.5 High 5.5 C30+43.95 0.61 1.48 56.05 35.54 81.66 54 2.5/3/1.5 High 7 R-3053A 43.01 4.2812.49 27.65 47.26 71.56 55 2.5/1.5/1.5 High 6.5 R-3053A 44.13 3.16 8.9024.50 46.64 75.77 56 2.5/2.63/1.5 High 6.63 R-3053A 43.30 2.51 7.3868.06 38.34 64.14 57 0/1.2/1 Medium 2.2 C30+ 44.87 9.01 25.44 78.0243.85 78.37 58 2.5/1.5/1 High 6.5 R-3053A 43.63 2.28 7.15 42.09 52.6985.38 59 2.5/1.88/0.5 Medium 4.88 R-3053A 43.68 5.42 13.57 39.98 55.2887.02 60 2.5/3/1.5 Medium 7 C30+ 43.29 2.74 8.94 36.79 56.22 88.54 612.5/1.5/0.5 High 4.5 R-3053A 43.79 2.30 9.29 30.94 61.14 88.71 622.5/2.63/0.5 Medium 5.68 C30+ 43.18 3.29 13.58 42.36 72.26 94.03 632.5/3/1 Medium 6.5 C30+ 42.89 3.23 7.61 33.37 58.35 90.11 642.5/1.88/0.5 High 4.88 C30+ 43.87 4.32 17.27 57.02 80.53 94.79 652.5/1.88/1 Medium 5.38 C30+ 43.62 2.71 8.33 31.26 66.26 92.63 662.5/1.5/1.5 Medium 5.5 C30+ 43.83 1.68 7.29 66.10 59.68 91.4 67 2.5/3/1High 6.5 R-3053A 43.60 5.86 13.28 54.82 56.85 84.69 68 2.5/1.5/1 Medium5 R-3053A 44.34 3.26 9.47 69.23 78.01 91.74 69 2.5/3/1.5 High 7 C30+43.35 2.85 8.30 55.12 59.76 88.51 70 2.5/1.5/0.5 Medium 4.5 C30+ 44.372.15 5.31 67.25 77.14 93.11 71 2.5/1.5/1.5 Medium 5.5 C30+ 44.18 0.440.90 69.45 71.21 92.55 72 2.5/1.5/1 High 5 C30+ 44.31 1.72 6.32 85.5079.2 94.42 73 2.5/2.63/1 High 6.13 C30+ 43.36 3.38 13.43 89.32 82.9896.26 74 2.5/3/0.5 Medium 6 R-3053A 43.51 4.07 9.05 90.70 82.75 93.87 752.5/3/0.5 High 6 R-3053A 43.24 3.78 13.85 91.23 74.14 94.05 76 0/3/1.5High 4.5 R-3053A 44.55 25.96 38.72 65.53 61.00 80.50 77 0/1.2/1 High 2.2R-3053A 45.08 23.08 45.43 82.67 68.06 82.12 78 0/1.7/0.5 High 2.2R-3053A 44.99 35.67 58.86 91.01 79.05 90.70 79 0/1.2/1 Medium 2.2R-3053A 44.97 9.49 25.69 78.55 57.38 78.98 80 0/1.7/0.5 Medium 2.2R-3053A 44.72 14.48 27.96 72.18 53.96 78.22 81 0/1.7/0.5 High 2.2 C30+44.95 19.98 39.56 82.17 62.24 88.29 *“L” refers to lignin, “P” refers to“polymer” and “W” refers to wax.

The samples can be segmented into 3 sections based on the 3 day releaseof oven test results as follows: Examples 41-50 (less than 30% release),Examples 51-57 (30% to 50% release), and Examples 58-62 (above 50%release). The results are also illustrated graphically in FIG. 5. Therewere some positive results in both the 24 hour accelerated release testas well as the 7 day oven test.

Examples 82-99 PLA with/without Lignin

In these examples, the total coating was varied between 6.5 to 8 wt. %.Lignin (lignin-1, L) was varied between 0 and 3 wt. %, PLA (P) wasvaried between 2 and 5 wt. %, and the sealant (W) was varied between 1.5and 2 wt. %. The coating formulations and thed release test results areshown in Table 6. The results are also illustrated graphically in FIG.6.

TABLE 6 Accelerated Nutrient 7-Day (Oven L/P/W Coating PLA Sealant NRelease Test, % Test), % Ex. (wt. %) (wt. %) Type Type (wt. %) 2 hr 4 hr24 hr 3 Day 7 Day 82 3/2/2 7 (Low) C30+ 43.85 0.35 0.37 24.24 46.6981.42 83 2.5/3/1.5 7 (High) C30+ 43.23 3.11 10.34 70.58 54.69 88.15 840/5/1.5 6.5 (High) C30+ 43.26 14.59 31.68 90.01 52.84 74.60 85 2.5/3/1.57 (Low) C30+ 43.82 5.45 11.23 65.93 69.72 92.94 86 3/3/1.5 7.5 (High)R-3053A 43.09 1.85 7.24 54.86 69.50 87.58 87 2/4/1.5 7.5 (High) C30+43.28 8.94 22.80 68.21 62.97 89.85 88 3/2/1.5 6.5 (High) R-3053A 44.083.63 9.11 59.16 70.01 87.32 89 3/2/2 7 (High) R-3053A 43.35 1.32 3.3651.73 61.77 87.12 90 3/2/2 7 (Low) C30+ 43.45 0.96 1.13 39.03 68.3192.82 91 3/3/1.5 7.5 (Low) R-3053A 43.12 13.85 26.58 73.62 77.12 94.6692 2/4/1.5 7.5 (High) R-3053A 43.28 6.05 25.81 67.62 83.31 93.70 932/4/1.5 7.5 (Low) R-3053A 43.09 13.84 45.83 94.26 95.92 97.13 94 2/4/1.57.5 (Low) C30+ 43.00 9.39 27.01 77.72 90.96 98.39 95 0/5/1.5 6.5 (High)R-3053A 43.16 19.77 50.83 81.29 84.50 89.56 96 0/5/1.5 6.5 (Low) R-3053A43.09 52.22 74.07 100.00 87.57 92.05 97 0/5/1.5 6.5 (Low) C30+ 43.5563.90 84.31 90.63 91.73 94.30 98 3/2/1.5 6.5 (High) R-3053A 43.63 3.9213.94 76.67 97.17 96.63 99 3/3/2 8 (Low) C30+ 42.89 6.84 12.46 49.8573.24 91.85 *“L” refers to lignin, “P” refers to “polymer” and “W”refers to wax.

The 4 hour measurements of the 24 hour accelerated release test and the3 day measurements of the oven test yielded some positive results(approximately 50% release). Based on the 3 day release test results,the data are segmented into 3 sections: Examples 82-84 (release lessthan 55%), Examples 85-90 (release between 55 and 70%), and Examples91-99 (release above 70%). The data show that the 7 day release testresults at 100° F. (38° C.) were higher than desired rate.

Examples 100-113 PBS-PLA Blend with/without Lignin

In these examples, the total coating was varied between 3.5 to 7.5 wt.%. Lignin (lignin-1, L) was varied between 0 and 3 wt. %, PLA was variedbetween 1 to 4 wt. %, PBS was varied between 1 and 2 wt. %, and thesealant (W) was varied between 1.5 and 2 wt. %. The coating formulationsand the nitrogen release test results are shown in Table 7. The resultsare illustrated graphically in FIGS. 7 and 8.

TABLE 7 Accelerated Nutrient 7-Day L/PLA/PBS/W* Coating Sealant NRelease Test, % (Oven Test), % Ex. (wt. %) (wt. %) Type (wt. %) 2 hr 4hr 24 hr 3 Day 7 Day 100 3/1/2/1.5 7.5 R-3053A 42.87 0.00 0.00 3.83 2.856.65 101 3/1.5/1.5/1.5 7.5 R-3053A 43.07 0.00 0.00 0.49 0.08 4.93 1020/1.5/1.5/2 5 C30+ 43.98 0.75 1.50 4.66 1.89 7.70 103 0/1.5/1.5/2 5 C30+43.83 0.03 0.39 2.81 0.66 7.27 104 0/2/2/1.5 5.5 C30+ 43.63 0.16 0.353.72 0.00 6.85 105 3/1.5/1.5/1.5 7.5 R-3053A 42.74 0.89 1.05 30.15 4.3611.26 106 3/1/2/1.5 7.5 R-3053A 42.77 0.00 0.00 0.84 0.00 11.63 1073/1/2/1.5 7.5 R-3053A 42.73 0.44 0.44 32.83 2.92 17.97 108 0/4/2/1.5 7.5R-3053A 42.66 2.26 3.20 16.67 10.62 18.49 109 0/1.5/1.5/2 5 R-3053A44.00 0.39 1.49 7.35 8.37 18.56 110 0/1/1/1.5 3.5 C30+ 44.67 1.31 1.8929.81 4.96 15.95 111 0/1/1/1.5 3.5 C30+ 44.62 0.45 0.92 8.27 2.87 16.51112 0/2/2//1.5 5.5 C30+ 43.66 0.78 1.50 9.03 3.17 12.09 113 0/2/2//1.55.5 R-3053A 43.34 0.85 1.53 7.34 5.44 12.98 114 3/1/1/1.5 6.5 R-3053A43.18 0.82 0.93 32.80 14.36 32.58 115 3/1/2/1.5 7.5 R-3053A 43.34 0.000.00 7.26 4.88 31.48 116 3/1.5/1.5/1.5 7.5 R-3053A 42.72 0.40 0.55 4.099.71 37.37 117 3/1/1/1.5 6.5 R-3053A 43.47 0.20 0.55 8.84 10.34 39.89118 3/1.5/1.5/1.5 7.5 R-3053A 42.99 0.00 0.00 74.05 2.19 35.67 1193/1/1/1.5 6.5 R-3053A 43.56 0.93 1.07 79.42 8.47 32.53 120 3/1/2/1.5 7.5R-3053A 43.03 0.00 0.00 66.47 0.34 31.24 121 0/1.5/1.5/2 5 R-3053A 43.743.00 6.02 24.76 20.96 30.79 122 0/1/1/1.5 3.5 R-3053A 44.48 2.64 6.9335.30 22.96 39.34 123 0/1/1/1.5 3.5 R-3053A 44.22 0.70 2.80 19.80 18.1434.21 124 0/2/2/1.5 5.5 R-3053A 43.54 1.29 2.27 8.82 9.98 22.23 1253/2/1/1.5 7.5 C30+ 42.68 0.88 1.93 41.18 24.38 58.31 126 3/2/1/1.5 7.5R-3053A 42.93 1.85 3.70 78.72 16.11 49.05 127 3/2/1/1.5 7.5 C30+ 42.990.63 0.63 79.11 4.82 43.97 128 0/4/2/1.5 7.5 C30+ 43.00 6.57 11.77 42.3834.07 49.28 129 0/2/1/1.5 4.5 C30+ 44.08 7.19 13.77 53.82 31.50 46.60130 0/2/1/1.5 4.5 R-3053A 43.76 3.01 7.95 41.00 30.51 52.81 1310/2/1/1.5 4.5 C30+ 44.18 5.14 11.52 61.25 20.60 40.65 132 3/2/1/2 7R-3053A 43.03 1.92 5.04 51.84 43.74 71.72 133 0/2/1/2 5 R-3053A 43.7911.43 26.73 71.60 64.18 78.84 134 3/2/1/1.5 7.5 R-3053A 42.92 2.96 7.6460.97 49.54 74.10 135 3/2/1/1.5 7.5 C30+ 43.41 3.35 8.95 69.52 46.0180.98 136 3/2/1/1.5 7.5 R-3053A 43.32 2.64 7.25 43.78 38.32 67.08 1373/2/1/1.5 7.5 C30+ 43.13 3.08 8.03 61.45 54.86 85.40 *“L” is lignin, “W”is waxThe samples can be segmented into 5 sections based on the 7 day oventest measurements as follows: Examples 100-104 (less than 10% release),Examples 1-5-113 2 (10% to 20% release), Examples 114-124 (20 to 40%release), Examples 125-131 (40 to 60% release), and Examples 132-137(above 60% release).

Examples 138-150 PLA/PBS blend

Additional PLA/PBS blends were tested. Polymers were coatedsimultaneously. Formulations and results are shown in Table 8. The 7 dayoven test results are also illustrated graphically in FIGS. 9-11.

TABLE 8 14-Day Release test, % L/PLA/PBS/W* Coating Sealant Sealant N(Oven Test) Ex. (wt. %) Polymer Type (wt. %) Type (wt. %) (wt. %) 3 Day7 Day 14 Day 138 3/0/3/1.5 PBS (medium) 7.5 R-3053A 1.5 42.99 5.75 13.4237.08 139 3/2/1/2 PLA(high)/ 8 R-3053A 1.5 43.03 43.74 71.72 90.06PBS(medium) 140 3/1.5/1.5/1.5 PLA(high)/ 7.5 R-3053A 1.5 42.72 9.7137.37 80.39 PBS(medium) 141 3/1/2/1.5 PLA(high)/ 7.5 R-3053A 1.5 42.732.92 17.97 51.51 PBS(medium) 142 3/3/0/1.5 PLA(high) 6.5 R-3053A 1.543.09 54.86 69.50 87.58 143 3/0/3/1.5 PBS(high) 7.5 R-3053A 1.5 42.8622.09 37.98 53.23 144 3/1.5/1.5/1.5 PLA(high)/ 7.5 R-3053A 1.5 42.744.36 11.26 41.91 PBS(high) 145 3/1/2/1.5 PLA(high)/ 7.5 R-3053A 1.542.87 2.85 6.65 45.4 PBS(high) 146 3/3/0/1.5 PLA(high) 7.5 R-3053A 1.543.09 54.86 69.50 87.58 147 3/0/3/1.5 PBS(high) 7.5 R-3053A 1.5 42.8622.09 37.98 53.23 148 3/1.5/1.5/1.5 PLA(low)/ 7.5 R-3053A 1.5 43.07 0.084.93 48.58 PBS(high) 149 3/1/2/1.5 PLA(low)/ 7.5 R-3053A 1.5 42.77 0.0011.63 55.62 PBS(high) 150 3/3/0/1.5 PLA(low) 7.5 R-3053A 1.5 43.12 73.6277.12 94.66 **“L” refers to lignin and “W” refers to wax.

The data indicate that a combination of PBS (high) and PLA (low) as wellas a blend of PBS (high) and PLA (high) have a synergistic effect on thefertilizer nutrient release. For example, at a loading level of 3 wt. %,PBS (high) alone had a 7 day release of 37.98% (example 147) and PLA(low) alone had a 7 day release of 77.12% (example 150). In contrast,when a 1:1 blend of PBS (high) and PLA (low) or a 1:2 blend of PBS(high) and PLA (low) were used at a loading level of 3 wt. %, the 7 dayreleases were reduced to 4.93% and 11.63% respectively (examples 148 and149).

Examples 151-155 Lignin with/without Wax

Granular urea was coated with lignin with or without wax. The coatingformulations and results are shown in Table 9.

TABLE 9 Accelerated Nutrient 7-Day (Oven Lignin Polymer Sealant SealantRelease Test, % Test), % Ex. (wt. %) (wt. %) Type (wt. %) 2 hr 4 hr 24hr 3 Day 7 Day 151* 3.0 0 R- 1.5 53.54 92.75 100 *** *** 3053A 152* 3.00 C30+ 1.5 82.04 98.67 98.98 *** *** 153* 2.0 0 C30+ 0 100 100 100 ****** 154* 2.0 2.0 PBS C30+ 1.5 0.61 1.48 56.05 35.54 81.66 (high) 155*2.5 3.0 PLA C30+ 1.5 3.11 10.34 70.58 54.69 88.15 (high) *ComparativeexamplesAs shown in Table 9, lignin with or without wax showed 92.75% to 98.70%release at 4 hour accelerated nutrient release test. In contrast, whenthe coating contained PBS or PLA in addition to lignin, the 4 houraccelerated results were 1.48% and 10.34% respectively. The resultsindicate that lignin at these coating levels by itself does not providesustainable nutrient release.

Examples 156-175 Comparison between Sequential and Blend (Simultaneous)Coating

In these examples, the total coating was varied between 3.5 to 7.5 wt.%. Lignin (lignin-1) was either kept constant at 3 wt. % (Ex171-175) orwas absent from the coating (Ex156-170), PLA was varied between 1 to 2wt. %, PBS was varied between 1 and 2 wt. %, and the sealant was keptconstant at 1.5 wt. %. Granular urea was coated simultaneously orsequentially by spray coating.

The coating formulations and the nitrogen release test results are shownin Table 10. The results are also illustrated graphically in FIGS. 12and 13. The results indicate that blend coated urea performs better thansequentially coated urea for most of the cases based on the 7 dayrelease data. There are no significant differences for the 14 dayrelease data.

TABLE 10 14-Day Release test, % Polymer Sealant (Oven Test) Ex. PolymerType (wt. %) Type Coating N (wt. %) 3 Day 7 Day 14 Day 156 PLA (high)/2.0/1.0 C30+ polymers sprayed 42.68 24.38 58.31 89.81 PBS (med.)simultaneously 157 PBS (med)/ 1.0/2.0 C30+ polymers sprayed 43.23 27.3755.19 83.45 PLA (high) sequentially 158 PLA (low)/ 2.0/1.0 R-3053Apolymers sprayed 42.93 16.11 49.05 86.30 PBS (med.) simultaneously 159PBS (med.)/ 1.0/2.0 R-3053A polymers sprayed 43.04 54.19 78.36 94.20 PLA(low) sequentially 160 PLA (low)/ 2.0/1.0 C30+ polymers sprayed 42.994.82 43.97 87.41 PBS (med.) simultaneously 161 PBS (med.)/ 1.0/2.0 C30+polymers sprayed 42.96 22.19 52.11 83.14 PLA (low) sequentially 162 PLA(high)/ 1.0/1.0 R-3053A polymers sprayed 43.18 14.36 32.58 69.85 PBS(med.) simultaneously 163 PLA (high)/ 1.0/1.0 R-3053A polymers sprayed43.39 39.83 57.41 73.25 PBS (med.) sequentially 164 PLA (high)/ 1.0/2.0R-3053A polymers sprayed 42.87 2.85 6.65 45.4 PBS (med.) simultaneously165 PLA (high)/ 2.0/1.0 R-3053A polymers sprayed 43.14 40.09 60.73 74.14PBS (med.) sequentially 166 PLA (high)/ 1.0/1.0 R-3053A polymers sprayed43.34 4.88 31.48 82.43 PBS (med.) simultaneously 167 PLA (high)/ 1.0/1.0R-3053A polymers sprayed 43.35 74.49 86.58 95.24 PBS (med.) sequentially168 PLA (high)/ 1.0/2.0 R-3053A polymers sprayed 42.77 0.00 11.63 55.62PBS (med.) simultaneously 169 PLA (high)/ 2.0/1.0 R-3053A polymerssprayed 43.30 14.53 27.60 59.54 PBS (med.) sequentially 170 PLA (high)/1.0/1.0 R-3053A polymers sprayed 43.47 10.34 39.89 82.24 PBS (med.)simultaneously 171 PLA (high)/ 1.0/1.0 R-3053A polymers sprayed 43.8212.63 22.53 41.27 PBS (med.) sequentially 172 PLA (high)/ 1.0/2.0R-3053A polymers sprayed 42.73 2.92 17.97 51.51 PBS (med.)simultaneously 173 PLA (high)/ 2.0/1.0 R-3053A polymers sprayed 43.5312.75 29.15 45.44 PBS (med.) sequentially 174 PLA (high)/ 1.0/1.0R-3053A polymers sprayed 43.56 8.47 32.53 78.52 PBS (med.)simultaneously 175 PLA (high)/ 1.0/1.0 R-3053A polymers sprayed 43.8248.48 69.89 85.84 PBS (med.) sequentially

Examples 176-193 Recycled PLA/PBS Blend with or without Lignin

In these examples, different recycled PLA grades, PLA Repro pkg, PLARepro-box, PLA Repro-label, PLA 2500HP, and PLA 3100HP from Natureworkswere used. Formulation and results are shown in Table 11. The resultsare also graphically illustrated in FIGS. 14 and 15.

TABLE 11 Accelerated Nutrient Lignin PLA/PBS/W* Sealant Release Test, %7-Day (Oven Test), % Ex. (wt. %) Polymer Type (wt. %) Type 2 hr 4 hr 24hr 3 Day 7 Day 14 Day 176 3 PLA (Repro-pkg)/ 1.0/1.0/1.5 R-3053A 0.711.51 13.71 9.68 26.62 76.63 PBS(High) 177 3 PLA (Repro-box)/ 1.0/2.0/1.5R-3053A 0.18 0.30 4.42 1.19 5.55 45.17 PBS(High) 178 3 PLA (Repro-1.0/2.0/1.5 R-3053A 0.15 0.24 2.38 1.05 2.19 55.08 label)/PBS(Med) 179 0PLA (Repro-pkg)/ 1.5/1.5/2 R-3053A 3.26 6.18 28.60 35.63 50.90 67.20PBS(High) 180 0 PLA (Repro-box)/ 2.0/2.0/1.5 R-3053A 3.26 6.28 33.2831.95 47.11 60.85 PBS(High) 181 0 PLA (Repro- 2.0/2.0/1.5 R-3053A 2.334.52 16.99 11.57 17.77 31.51 label)/PBS(Med) 182 3 PBS (High)/PLA1.0/1.0/1.5 R-3053A 0.30 0.68 17.89 10.96 19.40 41.79 (2500HP) 183 3 PBS(High)/PLA 1.0/2.0/1.5 R-3053A 1.27 4.05 42.38 30.62 50.65 74.48(2500HP) 184 3 PBS (Med)/PLA 1.0/2.0/1.5 R-3053A 0.98 4.52 47.22 36.3258.50 83.97 (3100HP) 185 0 PBS (High)/PLA 1.0/1.0/2 R-3053A 7.68 13.3437.27 21.94 32.93 45.51 (3100HP) 186 0 PBS (High)/PLA 1.5/1.5/1.5R-3053A 12.24 21.03 51.88 25.51 39.88 52.88 (2500HP 187 0 PBS (Med)/PLA1.5/1.5/1.5 R-3053A 3.65 9.06 34.06 14.10 26.07 38.82 (3100HP) 188 3 PLA(2500HP)/ 1.0/1.0/1.5 R-3053A 0.36 1.14 17.21 9.98 21.60 59.46 PBS(High) 189 3 PLA (2500HP)/ 1.0/2.0/1.5 R-3053A 0.28 0.68 5.04 1.79 4.9424.52 PBS (High) 190 3 PLA (3100HP)/ 1.0/2.0/1.5 R-3053A 0.20 0.42 2.710.70 5.13 46.42 PBS (Med) 191 0 PLA (3100HP)/ 1.0/1.5/1.5 R-3053A 15.6424.35 49.07 36.86 50.41 65.81 PBS (High) 192 0 PLA (2500HP)/ 1.5/1.5/1.5R-3053A 18.10 30.23 62.51 38.09 54.75 68.56 PBS (High) 193 0 PLA(3100HP)/ 1.5/1.5/1.5 R-3053A 1.40 4.07 22.62 9.65 19.51 36.61 PBS (Med)*“W” is wax

The results indicate that recycled PLA can also be used in the coatingfor urea. However, the performance was not as advantageous as thesystems using virgin PLA (see Table 8).

Examples 194-197 Recycled PLA-CTA

Granular urea was coated with various recycled PLA-CTA coating systems.The coating formulations and the nitrogen release test results are shownin Table 12. The seven day and fourteen day release results are alsoillustrated graphically in FIGS. 16 and 17.

TABLE 12 Accelerated PLA/PBS/ Nutrient Release Lignin Wax Sealant Test,% 7-Day (Oven Test), % Ex. (%) Polymer Type (wt. %) Type 2 hr 4 hr 24 hr3 Day 7 Day 14 Day 194 0 PLA(2500HP)/CTA 1.5/1.5/1.5 R-3053A 1.40 2.4714.75 4.56 17.29 53.70 195 0 PLA(3100HP)/CTA 1.5/1.5/1.5 R-3053A 2.194.80 38.14 16.65 53.52 83.06 196 3 PLA X(2500HP)/CTA 1.5/1.5/1.5 R-3053A0.50 0.98 7.86 5.26 17.41 62.33 197 3 PLA(3100HP)/CTA 1.5/1.5/1.5R-3053A 0.45 1.10 5.03 2.21 9.91 70.41

The results indicate that recycled PLA/CTA blends can also be used inthe coating for urea. However, at 4.5 wt. % as well as 7.5 wt. % coatinglevels, PLA/CTA (see Table 3) blends performed superior to recycledPLA/CTA blends in retaining urea based on the 7 day oven test.

The singular forms “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise. “Or” means “and/or.” Theendpoints of all ranges directed to the same component or property areinclusive and independently combinable. The suffix “(s)” as used hereinis intended to include both the singular and the plural of the term thatit modifies, thereby including at least one of that term (e.g.,“colorant(s)” includes at least one colorant). “Optional” or“optionally” means that the subsequently described event or circumstancecan or cannot occur, and that the description includes instances wherethe event occurs and instances where it does not. Unless definedotherwise, technical and scientific terms used herein have the samemeaning as is commonly understood by one of skill in the art to whichthis invention belongs.

As used herein, a “combination” is inclusive of blends, mixtures,alloys, reaction products, and the like. Compounds are described usingstandard nomenclature. For example, any position not substituted by anyindicated group is understood to have its valency filled by a bond asindicated, or a hydrogen atom. A dash (“—”) that is not between twoletters or symbols is used to indicate a point of attachment for asubstituent. For example, —CHO is attached through carbon of thecarbonyl group.

All references cited herein are incorporated by reference in theirentirety. While typical embodiments have been set forth for the purposeof illustration, the foregoing descriptions should not be deemed to be alimitation on the scope herein. Accordingly, various modifications,adaptations, and alternatives can occur to one skilled in the artwithout departing from the spirit and scope herein.

1. A coated fertilizer comprising: a fertilizer granule; and a coatingdisposed on a surface of the fertilizer granule, wherein the coatingcomprises a poly(lactic acid); a second polymer comprising apoly(butylene succinate), a cellulose triacetate, or a combinationcomprising at least one of the foregoing; and a sealant.
 2. The coatedfertilizer of claim 1, wherein the sealant comprises a wax.
 3. Thecoated fertilizer of claim 1, wherein the second polymer comprisespoly(butylene succinate).
 4. The coated fertilizer of claim 1, whereinthe second polymer comprises cellulose triacetate.
 5. (canceled) 6.(canceled)
 7. The coated fertilizer of claim 1, wherein the nitrogencontent of the coated fertilizer is 42 wt % to 45 wt %, based on thetotal weight of the coated fertilizer.
 8. The coated fertilizer of claim1, wherein the coating comprises the poly(lactic acid), the secondpolymer, and the sealant in combination in a single layer.
 9. The coatedfertilizer of claim 1, wherein the coating comprises: a first layerdisposed on the fertilizer granule, wherein the first layer comprisesthe poly(lactic acid) and the second polymer; and a second layerdisposed on the first layer, wherein the second layer comprises thesealant.
 10. The coated fertilizer of claim 1, wherein the coatingcomprises: a first layer disposed on the fertilizer granule, wherein thefirst layer comprises the poly(lactic acid) or the second polymer; asecond layer disposed on the first layer, wherein the second layercomprises the second polymer or the poly(lactic acid), provided that thefirst layer is not the same as the second layer; and a third layerdisposed on the second layer, wherein the third layer comprises thesealant.
 11. (canceled)
 12. A method of manufacture of the coatedfertilizer of claim 1, the method comprising combining the poly(lacticacid), the second polymer, and the sealant to provide a coatingcomposition; and depositing the coating composition as a layer on aplurality of fertilizer granules to provide the coated fertilizer. 13.(canceled)
 14. A method of making the coated fertilizer of claim 1, themethod comprising: dissolving the poly(lactic acid) and the secondpolymer in a solvent to provide a solution; depositing the solution on afertilizer granule to form a first layer; and depositing a sealant onthe first layer-coated fertilizer granules to form a second layer.
 15. Acoated fertilizer comprising: a fertilizer granule; and a coatingdisposed on the fertilizer granule, wherein the coating compriseslignin, starch acetate, or a combination thereof; and a second polymercomprising a poly(lactic acid), a poly(butylene succinate), a cellulosetriacetate, a poly(caprolactone), a poly(butylene terephthalateadipate), a cellulose acetate, or a combination comprising at least oneof the foregoing.
 16. The coated fertilizer of claim 15, wherein thecoating further comprises a sealant.
 17. (canceled)
 18. (canceled) 19.(canceled)
 20. The coated fertilizer of claim 15, wherein the secondpolymer comprises a combination of poly(lactic acid) and poly(butylenesuccinate).
 21. The coated fertilizer of claim 15, wherein the coatingcomprises: a first layer disposed on the fertilizer granule, wherein thefirst layer comprises the lignin, starch acetate, or a combinationthereof; a second layer disposed on the first layer, wherein the secondlayer comprises one or more second polymers; and optionally, a thirdlayer, wherein the third layer comprises an additional second polymer.22. The coated fertilizer of claim 21, wherein the coating furthercomprises a sealant layer disposed on the second layer or third layer,wherein the sealant layer comprises a sealant.
 23. The coated fertilizerof claim 21, wherein the second layer comprises poly(butylenesuccinate); and the third layer is present, and comprises poly(lacticacid).
 24. A method of making the coated fertilizer of claim 21, themethod comprising dissolving the lignin, starch acetate, or acombination thereof in a first solvent to provide a first solution;depositing the first solution on a plurality of fertilizer granules toform a first layer; dissolving the one or more second polymers in asecond solvent to provide a polymer solution; depositing the polymersolution on the first layer-coated fertilizer granules to provide asecond layer; optionally dissolving an additional second polymer in athird solvent to provide an additional polymer solution; and depositingthe additional polymer solution on the second layer-coated fertilizergranules to provide a third layer.
 25. (canceled)
 26. (canceled)
 27. Themethod of claim 24, wherein the second polymer comprises poly(lacticacid), poly(butylene succinate), poly (butylene terephthalate adipate),cellulose acetate, or a combination thereof, and the second solventcomprises dichloromethane.
 28. A method of manufacture of the coatedfertilizer of claim 21, the method comprising dissolving the lignin,starch acetate, or a combination thereof in a first solvent to provide afirst solution; depositing the first solution on a plurality offertilizer granules to form a first layer; dissolving at least twosecond polymers in a solvent to provide a second solution; anddepositing the second solution on the first layer-coated fertilizergranules to provide the coated fertilizer.
 29. (canceled)
 30. (canceled)31. A method of manufacture of the coated fertilizer of claim 21, themethod comprising contacting the lignin, starch acetate, or combinationthereof, and cellulose triacetate, poly(caprolactone), or a combinationthereof in a solvent to provide a coating composition; depositing thecoating composition on a plurality of fertilizer granules to provide thecoated fertilizer.
 32. (canceled)